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By W. N. Lacey, R. H. Dourson, B. H. Sage

The compositions of coexisting phases in the methane-propane-n-pentane system were determined at 160° and -2 20°F. throughout the two-phase region, at pressures above 500 lb. per sq. in. The experimental results permitted the calculation of gas-liquid equilibrium constants as well as the establishment of the critical behavior of this ternary system. Although many binary paraffin hydrocarbon systems have been investigated, the experimental work relating to the phase behavior of ternary paraffin hydrocarbon mixtures at elevated pressures is relatively scarce, being limited to a study of the meth-ane-propane-PL-pentane system at 100°F.l,2 However, Guter and co-workers have studied the phase behavior of the methane-ethane-ethylene system at relatively low temperatures. Information concerning the phase behavior of ternary systems is of value in predicting the behavior of the components in multicomponent systems, since the influence of pressure, temperature, and concentration may be individually ascertained. In the light of the importance of such information, the study of this ternary system was extended to higher temperatures in order to increase the field of temperature in which the data could be applied. Since all states encountered in this investigation are above the critical temperature of methane, the details of its phase behavior are not of direct significance. The properties of propane in the heterogeneous region were taken from a correlation3 based upon recently published data. The corresponding information for n-pentane was taken from experimentally measured vapor pressures and volumetric data.4 The rnethane-propane system has been studied throughout the two-phase region at temperatures above 70°F.,5 while the phase behavior of the propane-n-pentane system has been established for temperatures above 160°F.6 The volumetric and phase behavior of the methane-72-pentane system has been studied in detai1.7,8 The experimental measurements serve to establish with adequate accuracy the phase behavior of the components and of the constituent binary systems for this ternary system. It is believed that, with the exception of the measurements for the methane-propane system, the uncertainties in the earlier data relating to the pure substances and the binary mixtures are probably less than those associated with the values reported here. Method The methods and apparatus employed in this investigation have been described.137 In principle, the method involved the withdrawal of samples of the coexisting gas and liquid phases from a vessel containing a heterogeneous mixture of methane, propane and n-pentane. Provision was made so that

Jan 1, 1943

By David V. Ragone, Richard E. Balzhiser

The liquidus uranium concentration in the U-Bi system is given by the following expression for the temperature range 400° to 800°C: No break was observed in the curve over this temperature range. The partial molar enthalpy change for uranium in the liquidus reaction, UBi2— U + 2Bi, was found to equal 12,300 cal per g mole. Copper produced a continuous decrease in the liguihs uranium concentration at 600°C. The presence of copper in the solvent was observed to affect the uranium activity coefficient according to the following expression: duced no change in the liquidus combosition below 0.6 at. pct Pd. Higher palladium concentrations sharply depressed the uranium concentration. SOLUTE behavior in molten alloys has been shown to be strongly influenced by the presence of additional species. Much attention has been given to such phenomena in iron-base systems where a number of alloying elements and/or impurities are likely to be present in small but significant quantities. Frequently, the interaction of these solutes has altered their thermodynamic behavior to the extent that reaction equilibra are appreciably influenced. Consequently, much of the information available for binary behavior must be reevaluated when additional components are likely to be present. Similar interactions can be expected to occur in bismuth-base solvents. Interest in the use of bismuth solutions of uranium as reactor fuels has stimulated investigators to explore the effect of various elements on the liquidus uranium concentration. Criticality requirements necessitate close control of the uranium concentration which, at the anticipated operating temperature of 500°C, approaches saturation. Consequently, elements which suppress the liquidus concentration could produce serious reactivity problems. Since the fuel solution is cer- tain to contain additives, such as magnesium and zirconium, for corrosion inhibition as well as small concentrations of fission products and corrosion products, a better understanding of the possible interaction phenomena is mandatory. This need stimulated experimental programs at the Brookhaven National Laboratory and elsewhere to determine precisely the liquidus uranium concentration in the bismuth-rich portion of several ternary systems. Early experimental efforts were directed toward an accurate dcmtermination of the U-Bi liquidus over the temperature range from 300' to 800°c. As shown in Fig. 1, the results to date exhibit considerable scatter. The investigations of Bareis,' Teitel,2 Greenwood,3 and Cotterill and hon4 agreed well below 700°c. Greenwood and Teitel extended their studies to higher temperatures but failed to concur in their results. A more recent study by Schweitzer and weekss at Brookhaven National Laboratory between 300' and 725°c, produced values 15 pct lower

Jan 1, 1962

By D. A. Dahlstrom

Although the liquid-solid cyclone is a relatively recent innovation in the field of coal preparation, various authors have already indicated three distinct applications to operations encountered in the modern tipple. Driessen's articles and work at the Dutch State Mines exhibited its possibilities in the bene-ficiation of fine coal with apparently high efficiencies down to the 200-mesh fraction. l,2,3,4 Other publications point out its use as a recoverer, thickener, and preliminary dewatering agent of fine coal which in too many cases is being wasted due largely to former high operating cost limitations.M Finally, certain authors have emphasized the practicability of applying the cyclone to the elimination of coarse and fine solids from water slurries in the tipple in order to produce a water suitable for recycle purposes containing only minute particles far below the 200-mesh size.6 This would result in a closed water system for many cases, with its accompanying economic and operating advantages to locations where water quantity and quality problems are severe; better operation of washing equipment using a consistent water devoid of injurious fine particles; lowered maintenance costs due to the lesser abrasion resulting when the fine abraiding particles are removed; and the greater ease of disposing of refuse streams of reduced volume containing greater percentages of solids. While the three applications have been indicated to be feasible, only a meager amount of data is available on capacities and solid elimination eficiency as a function of design variables and cyclone friction loss. This information is essential for the optimum use and construction of the solid-liquid cyclone, and accordingly, work on the problem was initiated at Northwestern University. For the unfamiliar reader, briefly the cyclone consists of a cylindrical section mounted above a truncated cone. The feed nozzle enters the cylindrical ring tangentially with the underflow nozzle permitting discharge of the concentrated solids located at the apex of the cone. The overflow nozzle through which the clarified water exits is centered in the cylindrical section at the top of the cyclone. Half sections of experimental cyclones will be found in Fig la and 6. The feed slurry enters with a tangential velocity, thus creating a spiral pattern of high centrifugal force. The solid particles of sufficient size and gravity are ejected outward to the walls and spirally discharge to the underflow. Most of the water with uneliminated fine solids moves radially inward along the path of the outer

Jan 1, 1950

By Robert B. Fulton, Gill Montgomery

Fluorspar is the commercial name for fluorite, a mineral that is calcium fluoride, CaF2. The name, derived from the Latin word fluere (to flow), refers to its low melting point and its early use in metallurgy as a flux. It is the principal industrial source of the element fluorine. Cryolite, sodium aluminum fluoride, Na3AlF6, is a rare mineral which has been found in commercial quantities only in Greenland. The natural material has been supplanted by synthetic cryolite for its principal industrial use in the manufacture of aluminum. History Fluorspar was used by the early Greeks and Romans for ornamental purposes as vases, drinking cups, and table tops. Various peoples, including the Chinese and the American Indians, carved ornaments and figurines from large crystals. Its usefulness as a flux was known to Agricola in sixteenth century Europe. Fluorspar mining began in England about 1775 and at various places in the United States between 1820 and 1840. Production grew substantially following the development of basic open-hearth steelmaking, wherein it is used as a flux. Use was stimulated by growth of the steel, aluminum, chemical, and ceramic industries, particularly during World Wars I and II. Fluorocarbons entered the picture in 1931. The use of anhydrous hydrogen fluoride (HF) as a catalyst in the manufacture of alkylate for high octane fuel began in 1942. Differential flotation for separating fluorspar from galena, sphalerite, and common gangue minerals in the 1930s, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940s were outstanding technological advances that facilitated increased production. Recently, pelletizing and briquetting of flotation concentrates for use in steel furnaces and the development of flotation schemes for beneficiating ores containing abundant dolomite and barite have been major improvements in the industry. Uses of Fluorspar Fluorspar is used to make hydrogen fluoride, also called hydrofluoric acid, an intermediate for fluorocarbons, aluminum fluoride, and synthetic cryolite. It is used as a flux in the steel and ceramic industries, in iron foundry and ferroalloy practice, and has many minor specialized uses. Hydrogen fluoride (HF) is produced by reacting acid grade (97% CaF2) fluorspar with sulfuric acid in a heated kiln or retort to produce HF gas and calcium sulfate. After purification by scrubbing, condensing, and distillation, the HF is marketed as anhydrous HF, a colorless fuming liquid, or it may be absorbed in water to form the aqueous acid, usually 70% HF. Synthetic cryolite, organic and inorganic fluoride chemicals, and elemental fluorine are made from hydrofluoric acid. The acid itself is important in catalysis in the manufacture of alkylate, which is an ingredient in high-octane fuel for aircraft and automobiles, in steel pickling, enamel stripping, glass etching and polishing, and in various electroplating operations. The manufacture of one ton of virgin aluminum requires about 50 to 60 lb of fluorine content in synthetic cryolite and alumnium fluoride. This quantity, through improved technology and recovery practices, is being lowered significantly.

Jan 1, 1983

By L. W. Holm, A. K. Csaszar

A series of laboratory experiments was conducted in which oil was displaced from a porous medium by water-driven slugs of alcohols or similar solvents. The solvents used were soluble to some degree in both oil and water and covered the range of solubilities from complete solubility in oil to complete solubility in water. Displacement experiments were conducted on 2-and 3%-in. in diameter consolidated cores and 1-and 2-in. in diameter unconsolidated sand packs. The cores and sand packs ranged in length from 1 to 30 ft, and they were saturated with brine and crude or refined oils. The solvents used included ethyl alcohol, isopropyl alcohol (IPA), tertiary butyl alcohol (TBAI, secondary butyl alcohol (SBA), n-amyl alcohol (NAA), methyl ethyl ketone, acetone and others. It was found that all of the oil present in a porous medium could be miscibly displaced by injecting a slug of mutual solvent and driving it with water. The oil-recovery efficiency was dependent upon (1) the relative solubilities of the solvent in oil and water, and (2) the distance traversed by the flood. For complete oil recovery from cores, a smaller amount of a preferentially oil-soluble solvent was required, compared to the amount of preferentially water-soluble solvent needed. The size of the solvent slug required varied inversely with the linear flooding-path length raised to the 0.65 power. Water-driven dual solvent combinations (an oil-soluble solvent slug followed by a water-soluble solvent slug) were found to effect complete oil recovery with less total solvent than any single solvent used. In these dual-solvent displacement experiments, the slug size required varied inversely with length raised to the 0.55 power. Based upon the experimental results, a theory was developed to describe the displacement of oil and water by mutual solvents, and equations are presented to predict the production history in a linear system. These equations take into account the properties of the solvents and the porous medium. INTRODUCTION Oil-recovery processes which utilize displacing fluids that are miscible with the reservoir fluids have been studied extensively in recent years. Because of the poor contact efficiency and high pressure requirements of the LPG-gas displacement process there has been considerable interest in the alcohol-water process, and a number of studies have been made on the recovery of oil through the use of solvents which are mutually soluble in oil and water. An investigation by Sievert, Dew and Conleyl indicated that the use of mutual solvents would be limited because the presence of water in a porous medium would cause a phase break in the leading edge of the displacing solvent. Their study also showed that, in consolidated cores containing. only oil, the displacement of oil by a water-driven mutual-solvent slug of tertiary butyl alcohol (TBA) was affected by the viscosity ratios of the fluids involved. Gatlin and slobod3 concluded that an isopropyl alcohol (IPA) slug acts as a miscible piston, completely displacing both oil and water until the alcohol content of the mixing zone falls below the concentration necessary to maintain miscibility. Their study was conducted on uniform unconsolidated sand packs. They concluded further that IPA could be used effectively to recover oil from a watered-out sand. In a paper by Taber, Gamath and Reed4 relating an investigation on sandstone cores, it was stated that the displacement of oil by mutual solvents, particularly IPA, was not a miscible displacement and that no improvement in efficiency could be expected with increase in flooding-path length. However, their analytical analysis of the displacement mechanism using TBA is, in fact, one which indicates that the displacement is controlled by miscible mixing. They suggested that the lack of improvement in efficiency with flooding - path

By C. Bezemer, I. Havenaar

An investigation was carried out on the dynamic liltration behavior of drilling fluids. In a set-up consisting of a porous pipe through which the drilling mud was circulated, dynamic liltration rates and cake thicknesses were determined as a function of flow rate and filtration time. Eventually, a state of equilibrium was reached; i.e., both cake thickness and filtration rate attained constant values. Concurrently, dynamic filtration tests were carried out in a simple dynamic filter apparatus where mud flow was similar to that in a rotational vismmeter. In both arrangements the relation between equilibrium liltration data and rate of shear at the cake surlace was studied. Filter pipe and dynamic filter apparatus were lound to give identical relations. It was therelore concluded that the latter apparatus, which is suitable lor routine measurements on small amounts of mud, could be used to determine the dynamic liltration behavior of mud under borehole flow conditions. Some data are presented on the effect of filtration pressure and temperature on equilibrium filtration rate and cake thickness. INTRODUCTION In oil well drilling, the drilling fluid used generally forms a mud cake on the permeable sections of the borehole wall while filtrate is lost into the formation. As to the conditions under which this filtration process takes place, a distinction should be made between static mud filtration (mud is not circulating) and dynamic mud filtration (mud is circulating). In recent years several investigatorsl-5 have studied the process of dynamic mud filtration about which little had previously been known. This type of filtration is the subject of this paper which confirms several findings of previous investigators. It differs from already published works, however, in the following respects. 1. It contains a description of a simple laboratory apparatus developed for dynamic filtration measurements on small amounts of mud. 2. The effect of rate of shear at the cake surface on dynamic filtration has been studied. As a result of this study, dynamic filtration data pertaining to the borehole conditions of mud flow can be found from laboratory tests. 3. Some data are presented on the effect of filtration pressure and temperature on dynamic filtration. The work was limited to a small number of muds. No attempt was made to compare data on API filtrare loss with dynamic filtration rates. Previous workers have clearly shown that no correlation exists between static and dynamic filtration rates. EXPERIMENTAL ARRANGEMENT To establish whether the effect of mud flow conditions on dynamic filtrations is governed by the rate of shear at the cake surface, two different types of mud flow were used. In this connection the experiments were partially conducted by means of a porous pipe through which mud was circulated, partly in a dynamic filter apparatus which somewhat resembles a rotational viscometer. In both cases the flow conditions of the mud were well defined, thus making it possible to-calculate rates of shear at the cake surface. The filter pipe was 200 cm long with an internal diameter of 3 cm. Its perforated wall was covered on the inside with filter cloth on which the mud cake could form. Mud was pumped through the pipe at linear rates varying from 20 to 186 cm/sec. The required filtration pressure was obtained by means of a lack-pressure valve downstream of the filter pipe. In this arrangement the type of flow existing in the borehole is reasonably well simulated. The dynamic filter apparatus (Figs. I. and 2) consists mainly of two concentric cylinders with a clearance of about 0.5 cm. The outer cylinder (rotor) can be rotated at rates up to 1,000 rpm. The outer surface of the inner cylinder (radius about 2.5 cm) is covered with filter cloth or paper supported by copper gauze. The two cylinders are mounted inside a pressure

Jan 1, 1967

By Kendall E. Born

Production of crude oil in Tennessee during 1942 was approximately 8600 bbl., a decrease of 6500 bbl. from the production of 1941, and the lowest since 1934. As usual, the greater part of the production was from the Mississippian limestone pools in Scott and Morgan Counties. Some half dozen wells in Fentress and Clay Counties pumped intermittently produced about 1000 barrels. Natural gas was marketed from wells in Morgan and Fentress Counties for consumption in the Sunbright and Jamestown areas respectively. Figures are not available for the Morgan County production but 7,378,000 cu. ft. of natural gas was produced in the Jamestown gas field from six wells. The production of oil by counties is shown in Table I. Developments Drilling activities reached the lowest ebb since 1933. Only 10 wells were spudded during the year, one of which was drilling on Dec. 31, 1942. Of the nine completions, two were gas wells in the proven area south of Jamestown in Fentress County and seven were dry holes. The total footage drilled during the year was 14,198 ft.; the average depth of wells was 1578 ft. The completions are listed in Table 2. The distribution of tests according to physiographic divisions is given in Table 3. East Tennessee.—One well was drilled to 4219 ft., the second deepest well in the state, in Campbell County. The test was in the highly disturbed Valley and Ridge Province, an area long considered the most unfavorable in the state for the accumulation of oil and gas. Cumberland Plateau.-—There were no completions in the Cumberland Plateau area, although an old well drilled deeper found oil from 935 to 965 ft. in the Mississippi lime. This test has created a considerable amount of interest in the area and an active leasing campaign was underway early in 1943. Eastern Highland Rim.—Five completions on the Eastern Highland Rim brought in two small gas wells in Fentress County, which will be used to augment the supply for Jamestown. The producing horizons are shaly limestones of Ordovician (Trenton) age. Two wells in this area were drilled to the upper part of the Knox dolomite group. The most significant test during the year was the Stanolind Oil and Gas Company's test in Putnam County. This well, on a well-defined surface structure, was abandoned in the upper Knox dolomite group at 2130 ft. A show of oil was logged in the Knox at 1653 to 1661 ft. Northern Highland Rim.—Three tests widely separated in the Northern Highland Rim were dry.

Jan 1, 1943

By Kendall E. Born

Production of crude oil in Tennessee during 1942 was approximately 8600 bbl., a decrease of 6500 bbl. from the production of 1941, and the lowest since 1934. As usual, the greater part of the production was from the Mississippian limestone pools in Scott and Morgan Counties. Some half dozen wells in Fentress and Clay Counties pumped intermittently produced about 1000 barrels. Natural gas was marketed from wells in Morgan and Fentress Counties for consumption in the Sunbright and Jamestown areas respectively. Figures are not available for the Morgan County production but 7,378,000 cu. ft. of natural gas was produced in the Jamestown gas field from six wells. The production of oil by counties is shown in Table I. Developments Drilling activities reached the lowest ebb since 1933. Only 10 wells were spudded during the year, one of which was drilling on Dec. 31, 1942. Of the nine completions, two were gas wells in the proven area south of Jamestown in Fentress County and seven were dry holes. The total footage drilled during the year was 14,198 ft.; the average depth of wells was 1578 ft. The completions are listed in Table 2. The distribution of tests according to physiographic divisions is given in Table 3. East Tennessee.—One well was drilled to 4219 ft., the second deepest well in the state, in Campbell County. The test was in the highly disturbed Valley and Ridge Province, an area long considered the most unfavorable in the state for the accumulation of oil and gas. Cumberland Plateau.-—There were no completions in the Cumberland Plateau area, although an old well drilled deeper found oil from 935 to 965 ft. in the Mississippi lime. This test has created a considerable amount of interest in the area and an active leasing campaign was underway early in 1943. Eastern Highland Rim.—Five completions on the Eastern Highland Rim brought in two small gas wells in Fentress County, which will be used to augment the supply for Jamestown. The producing horizons are shaly limestones of Ordovician (Trenton) age. Two wells in this area were drilled to the upper part of the Knox dolomite group. The most significant test during the year was the Stanolind Oil and Gas Company's test in Putnam County. This well, on a well-defined surface structure, was abandoned in the upper Knox dolomite group at 2130 ft. A show of oil was logged in the Knox at 1653 to 1661 ft. Northern Highland Rim.—Three tests widely separated in the Northern Highland Rim were dry.

Jan 1, 1943

By E. J. Rapperport, J. P. Pemsler

We have made calculations to evaluate the sensitivity of atomic absorption as a technique to measure vapor pressure changes with temperature. Our conclusion, supported by the experimental findings presented in this work, is that the ultimate sensitivity of the technique is well below lo-' Torr. This magnitude of vapor pressure sensitivity makes the method extremely attractive for thermodynamic studies. Atomic absorption techniques have been used previously in this connection by Scatchard and Boyd' and by vidale2 with a much lower sensitivity reported. Scatchard and Boyd's work measured cadmium pressure over Ag-Cd alloys in the range 0.02 to 0.3 Torr, and Vidale estimated that sensitivities of only 10"5 to 10"6 Torr are to be expected. Atomic absorption appears to be particularly well-suited to thermodynamic studies for several reasons: A) It is extremely sensitive; our experiments indicate an ability to measure vapor pressure changes of 10"9 Torr. B) It is highly selective; there is seldom interference among the resonant wavelengths of the various species. C) It may be performed in an absorption cell under static conditions. This alleviates such problems as surface impoverishment of alloys, attainment of equilibrium, and temperature measurement and control. D) Simultaneous, or near-simultaneous, vapor pressure measurements may be made for several elements in a given system. Experimental. The physical basis of the technique is the highly selective absorption of particular wavelengths by specific atomic species. In most atomic absorption work the element of interest is incorporated into a hollow cathode lamp to provide a characteristic spectral source of high intensity. The spectra lines characteristic of the element in the cathode are attenuated by atoms of that element in the radiation path. Radiation from silver or cadmium hollow cathode lamps was directed along a path containing a 10-cm evacuated silica cell. The cell was positioned within a silica windowed furnace and contained silver, cadmium, or an Ag-Cd alloy. As the furnace temperature was elevated, the number of atoms of the absorbing element in the vapor phase within the cell rose, and the resonant radiation was increasingly absorbed. Intensities were measured by passing the radiation through a Techtron Model AA-4 one-half meter grating atomic absorption spectrometer equipped with a photo-multiplier detector. In order to minimize instabilities in the source, the hollow cathodes were allowed to warm up for several hours and were run at only 2 5 to 30 pct of their maximum rated amperage. In addition the attenuated beam was monitored before and after each reading. The attenuation of resonant wavelengths may be related to vapor pressure by the following relationships.

Jan 1, 1969

By J. E. Gould, H. J. Hand

Many independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types. In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final de-oxidation. In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding overdeoxidation to minimize the amount of inclusions present and to make as sound a steel as possible. For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved. While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or low FeO values. The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests. With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishiug the state of oxidation at a given time. Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors. Data obtained are from actual iurnace operations, the metal test being of the I spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States I Steel Corporation. This method of taking open-hearth metal temperature was invented by Collins and Oseland,l and was developed into its present form by L. 0. Sordahl,2 of the Research Laboratory. The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications.3,4,5 lag components were obtained by chemical analysis. Data were taken from four 165-net-ton furnaces during the working period of the heat. Recognizing that additions of ore affect the metal FeO. no tests were included within 30 min. after ore additions. In all, 65 tests (48 heats) were used in this study.

Jan 1, 1942

By J. E. Gould, H. J. Hand

Many independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types. In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final de-oxidation. In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding overdeoxidation to minimize the amount of inclusions present and to make as sound a steel as possible. For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved. While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or low FeO values. The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests. With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishiug the state of oxidation at a given time. Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors. Data obtained are from actual iurnace operations, the metal test being of the I spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States I Steel Corporation. This method of taking open-hearth metal temperature was invented by Collins and Oseland,l and was developed into its present form by L. 0. Sordahl,2 of the Research Laboratory. The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications.3,4,5 lag components were obtained by chemical analysis. Data were taken from four 165-net-ton furnaces during the working period of the heat. Recognizing that additions of ore affect the metal FeO. no tests were included within 30 min. after ore additions. In all, 65 tests (48 heats) were used in this study.

Jan 1, 1942

By J. Chipman, J. B. Gero, T. B. Winkler

D. C. Hilty—This paper is a useful and timely addition to our store of quantitative data relating to manganese distribution between slag and metal in steel-making processes. For some time, many of us have suspected that the values of Kmn derived by Körber and Oelsen might be too low, and this paper now appears to confirm that suspicion. Application of the new constant to openhearth data should prove interesting. The manganese deoxidation curves of fig. 4 agree fairly well with direct measurements of isothermal solubilities of oxygen in liquid iron containing manganese that have recently been made at the Union Carbide and Carbon Research Labs., Inc. According to the solubility data just mentioned, however, the curves for 1550" and 1600°C lie much closer to each other than the authors have indicated. In other words, the solubility measurements suggest that the logarithm of the oxygen solubility is not a linear function of the reciprocal of the absolute temperature, as the authors have assumed for their calculations. It seems possible that this discrepancy may be due in part to the authors' use of the distribution coefficient, L,,, obtained from Taylor and Chipman's curve for the solubility of oxygen in iron as shown in fig. 2. Taylor and Chipman gave the equation of this curve as —6320 Log % 0 - ---T + 2.734 Their data, however, can be fitted equally well by a curve having the equation: 13.23 x104 1.18x10" Log % O = 36.350 -13.23x10 Moreover, this curve also fits the authors' oxygen distribution data somewhat better than does the linear curve of Taylor and Chipman. Its use in the derivation of Lo for calculation of the deoxidation curves by the authors' eq 15 causes the effect of temperature on the calculated curves of fig. 4 to agree quite well with the temperature effect that has been observed. An experimental determination of the temperature coefficient of the manganese reaction appears to be desirable. J. E. Stukel—Because the authors have done such an excellent job, my comments will be confined to additional information. Very shortly Professor T. L. Joseph and I will publish the results of a study of the reaction between molten manganese and silica. It was found that electrolytic manganese, melted in silica crucibles, reacted with the silica to form a silico-manganese alloy containing 18 pct silicon (1500°C) and a silica saturated MnO-SiO, slag. Therefore, the presence of silicon and its oxides in the Fe-Mn-0 system will affect the equilibrium. Carbon is also an important factor. The higher the carbon content of the iron the less ability manganese has to reduce silica. As a matter of interest, recently a study of the manganese equilibrium in carbon saturated iron and blast furnace slags was completed at Carnegie Institute of Technology. As a comparison to the present study, 2 to 5 hr were required to reach equilibrium and temperature was a much more important factor than slag composition in determining the (Mn)/(MnO) ratio. These results will also be published in the near future. It can be seen, therefore, that the results of this paper cannot be applied directly to openhearth studies without a degree of flexibility. J. Chipman (authors' reply)—With regard to the effect of silicon on the manganese constant, this effect is, of course, known. Much more data is needed in order to establish it accurately, and I hope we can look forward to having some accurate data on that. Mr. Hilty suggests that a three-term expression for the Taylor-Chipman solubility of oxygen in liquid iron might fit a little better than the two-term equation. I think that it would be too great a compliment to the precision of the data to employ a three-term equation, and I would still recommend the simple, two-term expression.

Jan 1, 1951

By Robert H. Richards

Very little has been published recently on this subject in the mining journals or proceedings of societies. The attention of experts has been diverted perhaps by the demands for pan amalgamation of refractory ores. Yet free milling ores occur in many localities, and it may be interesting to have on record some data as to details of running a small test-mill, especially as details of results do not seem to be accessible to stndents and investigators. Küstel, in 1863, under battery amalgamation, dismisses the subject by stating that "amalgamation on copper-plated platforms, troughs, and other copper fixings" is " very imperfect, and mostly abandoned." J. Arthur Phillips says, in 1867, under placer mining : " A well-amalgamated copper plate is considered as effective for

Jan 1, 1880

By A. S. Rhea

SALT-WATER disposal in the East Texas field by means of injection into the Woodbine sand is a relatively new procedure. The purpose of this paper is to present what has been accomplished to date in this field, with-out detailed discussion of other means of disposal, such as surface impound-ing for evaporation or release into surface streams. Subsurface disposal of salt water is still in an experimental stage in the East Texas field, and, though water can be injected into the Woodbine sand, the economic problem is not as yet solved. As past experience has been that fields producing from the Woodbine formation produce large quantities of salt water, it was assumed early in development of East Texas that it would be necessary to dispose of a tremendous quantity of salt water in the later periods of production. There has been a gradual increase in the amount of salt water pro-duced in the field, until at present it is about 200,000 bbl. per day from approximately 4400 wells. It is only natural to expect an increase in the number of wells producing water, as well as the amount of water produced in the future, and it has been estimated that if present practices con-tinue the production of salt water may ultimately be as much as 700,-000 bbl. per day. The Woodbine sand is found in the East Texas field at an average depth of 3650 ft. The oil-bearing portion of the sand lies between the depths of 3050 ft. below sea level, on the east edge of the field, and 3320 ft. below sea level on the west, which depth was the estimated original average oil-water contact. The Woodbine sand under the field has the form of a broad tilted wedge pinching out on the eastern side of the field and dipping gently into the East Texas Basin toward the west. The Woodbine sand in the East Texas field has an average porosity of approximately 25 per cent and is highly permeable, the average being about 1300 millidarcys.

Jan 1, 1940

By R. G. Vardiman, M. R. Achter

THERE has been interest recently in the conditions under which dislocation pipe diffusion may be observed. In order to extend the measurements to temperatures below Tm/2, where pipe diffusion becomes more important, a chemical sectioning technique was developed for silver single crystals which makes possible the removal of layers of 100A or less. The procedure is briefly as follows. Silver single crystals of 99.995 pct purity were cut in the form of discs t by 4 in., electropolished, and electropolated with Ag110 to about 1000A thickness. The thickness was determined by calibrating the activity with the weight of heavier platings, up to 10,000A. Both diffused and undiffused samples were sectioned in a two-step process. Reaction with a solution of iodine in alcohol formed a thin, even layer of AgI, which was then dissolved in a KCN solution. The reaction rate of the iodine solution varied slightly over a period of time, so that the thickness of the stripped layers, while quite even and regular for a given specimen, ranged from 65 to l00W for different specimens. This variation was checked by using a thickly plated standard with each run. Layer thickness was determined from undiffused samples by the point where the layer activity drops to half the maximum. This maximum intensity also provides, with appropriate corrections, the initial concentration per layer co. Because of the small penetration distances, it is necessary to use the exact solution of Fick's law for a source of finite thickness.' For a plating of thick- where c is the concentration at depth x. flj the error function, D the apparent diffusion coefficient, and t the time. The diffusion coefficient was obtained from the concentration-penetration data by extrapolating to x = 0 where c/co = erf h/2(Dt)1/2 Enough points were taken to impart confidence in the accuracy of the intersection, generally about ten layers. Four temperatures were used as in Table I. For best accuracy, t and h were chosen to give values of the parameter (Dt)1/2/h between 1.0 and 1.7. A typical concentration-penetration curve is shown in Fig. 1. The diffusion coefficients calculated from Eq. [I] are plotted in Fig. 2. For comparison, the high-temperature data of Tomizuka and sonder 2 which go down to 630°C are plotted as the solid line 2(a) from their expression D = 0.40 exp (-44,090/RT). Also for comparison, the lowest temperature point of Hoffman and Tumbull3 is plotted. It is apparent that our data diverge appreciably from the high-temperature extrapolation by 373°C. A better straight line fit for the low-temperature portion is obtained by subtracting the extrapolated volume diffusion coefficient from the apparent. or measured coefficient, and plotting the difference, curve (h) of

Jan 1, 1970

By G. P. Tiwari

Recrystallization and grain growth in thoria dispersed nickel and nichrome were recently studied by Webster as a function of temperature and deformation. The unexpected part of these results was that specimens which had received heavier deformation developed greater resistance to recrystallization. Retardation of recrystallization was accompanied by the formation of voids around thoria dispersion. To explain these results, Webster suggested that the formation of void around the particles increased the effective size of thoria particles. This resulted in greater impediment to the grain-boundary migration and as a consequence the recrystallization of the matrix is retarded. In the present note an alternative and more probable explanation for the effect of voids on recrystallization is presented. The exact mechanism of void formation in thoria dispersed nickel or nichrome is not known. However, it is reasonably certain that it must be preceded by the stress concentration in the matrix around thoria dispersion during the deformation.'' The resulting stress concentration must be sufficient enough to supply the surface energy for the new surfaces created. Further, the decrease in the strain energy of the matrix surrounding the potential void nucleus must be larger than the surface energy of the newly created surface. The release of strain energy due to formation of crack results in a strain free cylinder of the material around the voids.13 If the void formation is not localized, at few points only (as is the case here), this process may lead to considerable amount of release of strain energy of the matrix. The pattern of recrystallization behavior of single phase homogeneous matrix as well as the matrix having a second phase dispersion is same except for the fact recovery and recrystallization are more clearly delineated.14 In general, the recrystallization temperature is lowered (i.e., recrystallization is easier) with increase in the amount of cold work. This is due to the increase in stored energy in the matrix with increasing amount of deformation. If somehow there is a relaxation of strain energy in the matrix, the recrystallization should become difficult because of the decrease in the amount of stored energy available for recrystallization. Since the formation of voids leads to a decrease in the strain energy of matrix, the recrystallization of the matrix would be inhibited due to the formation of voids during deformation prior to recrystallization. It has been observed by earlier workers15'16 that the presence of preexisting voids in a matrix retards the recrystallization. The essential issue here is how do the voids act to produce this effect. If the voids influence recrystallization only by blocking the grain boundary migration, then the effect should be maximum when they are present almost exclusively along grain boundary. These conditions are obtained during high temperature deformation. However, the voids produced due to creep along grain boundary are not able to prevent recrystallization17 suggesting that they are not effective in blocking grain boundary movement. Recently it was shown by Davies and Williams that the voids can act as sinks for vacancies." As a result the processes dependent on vacancy diffusion like recovery, recrystallization, dislocation climb, and so forth, will be hindered. This fact may be responsible for inhibition of recrystallization during subsequent deformation and annealing cycles. It is to be noted here that there is a large difference between the density of voids in creep experiments and the other experiments where retarding effect of voids on recrystallization is seen. The voids in former may number up to l04 to l05 per sq cm whereas in latter cases the voids density is typically around 1010 to 1013 per sq cm. It appears that the decrease in supply of vacancies in creep is insufficient to adversely affect the recrystallization due to low void population. The author is grateful to P. Das Gupta and S. P. Ray for helpful discussions. Author's Reply D. Webster Tiwari appears to have misunderstood the nature of grain boundary-particle interactions. Tiwari (quoting Cahn) states that second phase particles become more effective as they become smaller, therefore as the voids in TDNiC make the thoria particles effectively bigger their ability to resist grain boundary movement is impaired. This particle size argument was originally proposed in the form of an equation by Zener 20 years agol9 and is not necessarily valid as is discussed below. However, assuming it is valid, it predicts a greater boundary restraining effect by smaller particles simply because their combined cross sectional area is greater at a constant volume. If the number of particles remains the same and their effective size increases, as in the present case, Zener's equation predicts a greatly reduced grain size. This is because the effect

Jan 1, 1970

By E. I. Alessandrini, A. U. Seybolt

Selective oxidation (preferential oxidation of a single alloy component) can be an important oxidation mode in the case of alloys such as Si-Fe, Al-Fe, and so on, when heat-treating in atmospheres of low oxygen potential. It was the purpose of this work to identify the oxide films formed on iron containing 31/4 pct Si at low oxygen potentials, and to make some observations on the H2O/H2 ratios required to form them. EXPERIMENTAL METHOD HYDROGEN of varying water content offers a very convenient method of establishing a wide range of oxidizing power, or oxygen potential. The method chosen to provide a desired H2O/H2 ratio was to nearly saturate hydrogen at room temperature by bubbling the gas through water at room temperature, and then to wring out the excess water by passing the wet gas through a long glass spiral immersed in a refrigerated liquid at a desired dew point. After oxidation, the samples were examined by electron diffraction in order to identify any film which might be present. PREPARATION AND TREATMENT OF SAMPLES The samples were prepared from a Si-Fe alloy made in the laboratory using electrolytic iron and 96 pct ferro-silico11, vacuum-induction melted, hot-rolled then cold-rolled to 0.015-in. thickness. After the cold-rolling the samples were annealed at 1000°C. Transmission Laue X-ray patterns showed very little evidence of preferred orientation, but it is likely that a weak texture could have escaped notice. The chemical analysis was as follows: 3.34 Si, 0.01 Al, 0.001 0, 0.006 C, 0.002 N. Before each sample was oxidized, it was polished through 4/0 emery paper, cleaned and dried using benzene, carbon tetrachloride, acetone, absolute alcohol, and ether. The method of oxidizing the samples was as follows: Samples about 1/2 by 1 by 0.015 in. were held in the upper, cool part of a vertical vacuum furnace until the desired temperature was established in the furnace, Fig. 1. The sample was then lowered into the uniform hot zone where it was heated quickly to the desired temperature, and subjected to hydrogen of controlled moisture content (dew point) as mentioned previously. Temperatures from 400" to 1000°C were used, and dew points from room temperature to —78°C were explored. In general, the runs lasted about 6 hr, but a few runs were of different duration, as will be indicated later. After the predetermined period of time had elapsed, the specimens were withdrawn by the hollow stainless steel-quartz holder to a cool zone at the top of the furnace. EXPERIMENTAL RESULTS The results are summarized in Table I. Most of the electron-diffraction patterns were obtained by glancing-angle reflection, but in a few cases it was possible to strip the oxide films from the surface by a total immersion in a 3 pct bromine-methanol solution. Some of the thinner stripped films yielded quite satisfactory transmission patterns. However, both diffraction techniques yielded the same results; the patterns while most frequently showing a (low) tridymite, also showed a (low) cristobalite in some cases. A few patterns showed evidence of both phases. Because of the known nonequilibrium behavior of silica, it is not surprising that both forms of silica could coexist on one sample. It was noted that at fairly low dew points such as —40°C, there was a tendency for diffuse diffraction rings, suggesting a very small crystallite size. Also some subsequent experiments to be reported later show that thin silica films can be amorphous.

Jan 1, 1959

By MAGNE MORTENSON

IN laboratory work and industrial tests it is important to set forth the results of research, clearly. This is generally achieved by means of some form of diagram or graphical illustration. The most common form for such graphs of flotation research is a simple chart with two curves for percentage and recovery of the concentrate. This may be quite useful, especially for minerals which may be floated: by means of one reagent in variable and another in constant amounts. If both reagents are used in variable quantities the process may be illustrated by means of several diagrams, .keeping one reagent constant in each series of tests. A more useful form of diagram for a. system with two variable - components (reagents) may be established by drawing a chart with the weights of the two reagents as .abscissas and ordinates. Every test is marked down -in the diagram with an indication of the extraction and concentration gained. In this diagram there are drawn lines for equi-extraction and equi-concentration of the mineral that is floated out in the - concentrate. The contour of these lines gives a relatively clear impression of the conditions for flotation by means of .the chemicals used. The best conditions are of course found in diagrams where the 'areas for maximum extraction and high conntration are coincident

Jan 1, 1931

By A. McLean, D. W. Gomersall, R. G. Ward

An experimental study has been made of the solubility of nitrogen in liquid iron and liquid Fe-C alloys using levitation melting and a rapid quenching device. Iron alloy droplets were equilibrated with nitrogen gas at 1 atm pressure, quenched, and analyzed. Previous techniques for studying the Fe-C-N system have produced data which me in marked disagreement. This disagreement is due largely to errors caused by reaction between the molten alloy and the crucible material. With the levitation procedure, errors from this source have been eliminated and precise solubility data obtained for temperatures between 1450° and 1750°C. C-N interactions in molten iron have been expressed in terms of first- and second-order free energy, enthalpy, and entropy parameters. ALTHOUGH the solubility of nitrogen in iron base alloys is in general small, the effects of nitrogen on the properties of steel may be quite profound. For most purposes nitrogen in finished steels is undesirable, particularly in the low-carbon grades, since on cooling to room temperature the solubility limit of nitrogen in the steel may be exceeded and this can lead to embrittlement and loss of ductility on aging. On the other hand, nitrogen can improve the work-hardening properties and machinability of steels while in certain stainless grades nitrogen is important in order to stabilize the austenite phase. It is, therefore, desirable that one should be able to predict the solubility of nitrogen in liquid iron alloys. To do this, information is required concerning the interactions between nitrogen and the various alloying elements which may be present in liquid iron. There have been several investigations of these effects in recent years1"7 and the interactions between nitrogen and many elements dissolved in liquid iron are now known to a high degree of precision at steel-making temperatures. Unfortunately, a number of iron alloy systems which are of interest in steelmaking have been difficult to deal with by the experimental techniques generally used for this type of investigation. Among the most important of these are the Fe-C alloys. In the past, two methods have been widely used for determining nitrogen solubilities: the Sieverts' technique, in which the amount of nitrogen required to saturate a given mass of liquid metal at a particular temperature and pressure is measured volumetrically, and the sampled-bath technique in which liquid metal held in a crucible is equilibrated with a gas phase containing a known partial pressure of nitrogen, and samples drawn from the melt are quenched and analyzed. These two methods have been discussed in detail elsewhere.5,8 With the Sieverts' technique, errors may be introduced from the following sources: i) Gas adsorption on metal films which have condensed on the cooler parts of the reaction chamber. ii) Uncertainty in the determination of "hot volume" calibrations. iii) Crucible-melt interaction, particularly if a gaseous reaction product is formed or if the melt becomes contaminated with material from the crucible walls. The sampled-bath method may also suffer from errors due to reaction between the melt and the crucible material. In addition, there is the possibility that gas may be lost from the sample during solidification and cooling. In the present investigation, the solubility of nitrogen in liquid iron alloys has been studied by means of a new technique based on the use of levitation melting equipment and a rapid quenching device. In addition to the fact that problems of the type outlined above are avoided, this particular approach has the following advantages: i) The high-frequency current induces vigorous stirring within the levitated droplet so that gas-metal equilibration is rapidly attained. ii) The gas phase surrounding the melt can be changed very quickly and is easily controlled. For example, a droplet may be levitated in helium, deoxidized in hydrogen, equilibrated with nitrogen, and quenched, within a period of 15 min. ii) Melts can be readily under cooled or superheated, thus extending the effective temperature range of an investigation and allowing temperature-dependent data to be determined with a high degree of precision. Excellent reviews of levitation melting techniques and their application to physical-chemistry studies at high temperature have been published recently by Jenkins et al.,9 Peifer,10 and Rostron.11 In the present investigation a levitation melting technique has been used to obtain data for the solubility of nitrogen in pure liquid iron and liquid Fe-C alloys at temperatures between 1450° and 1750°C. The solution of nitrogen in liquid iron can be described by the reaction:

Jan 1, 1969

In an address delivered at Atlantic City, N. T., Dec. 5, 1918, M. L. Requa, General Director, Oil Division of the United States Fuel Administration, said: We face a new era with all its uncertainties. We have arrived at the period of reconstruction and are face to face with the problems concerning which we have so often speculated during the past four years. In all this reconstruction work the United States must bear an important part. We are looked upon to lead the way, to blaze the trail and our actions will have a profound influence upon the rest of the world. If we are to succeed, even in part, we must not be ashamed to practise economy; we must not despise the clay of small things; the little savings; we must have the closest cooperation between Government and industry. Just as truly do we need civic awakening. All that we have ever fought for, the liberty of the world, is comprehended in the ballot; and yet how lightly we have held this great privilege! We need, if we are to reap in full the benefits of the past 18 mo., an awakened civic consciousness; a jealous guarding of government; a resolution that we will, each and all, perform to the full the duties imposed upon us by Democracy; that we will perform more completely the obligations resting upon us as citizens. During the war, industry, through sane cooperation and intelligent effort, has accomplished results possible of attainment in no other way. Government and industry have worked hand in hand and pointed the way o to future activities which, if realized, can but be most highly beneficial to all. If Government and industry are to fulfill their respective duties satisfactorily, it is obvious that there should be complete mutual confidence. Industry must not attempt to "put something over"-and Government must treat with industry upon the high plane that has characterized the public utterances of the President during the war. The individual who cannot conform to these high ideals should have no place in industry, and equally no place in Government. If the dignified and broad princi-

Jan 2, 1919